Azo dye polymers

ABSTRACT

Azo dye polymers useful in nonlinear optics contain as characteristic monomer units radicals of the formulae I, II, III and IV ##STR1## where D is the radical of a heterocyclic diazo component, 
     R 1  and R 2  are each hydrogen, C 1  -C 6  -alkyl or substituted or unsubstituted C 1  -C 6  -alkoxy, and R 2  may also be C 1  -C 4  -alkanoylamino, 
     R 3  is hydrogen, C 1  -C 6  -alkyl, C 5  -C 7  -cycloalkyl or C 3  -C 4  -alkenyl, 
     R 4  is hydrogen, deuterium, methyl, trideuterated methyl or chlorine, 
     R 5  is hydrogen or deuterium, 
     Y 1  and Y 2  are each substituted or unsubstituted C 2  -C 10  -alkylene, 
     W is oxygen, imino or C 1  -C 4  -alkylimino, and 
     X is hydroxyl, substituted or unsubstituted C 1  -C 6  -alkoxy, phenoxy, amino or mono- or di(C 1  -C 4  -alkyl)amino, 
     and have an average molecular weight of from 1,000 to 100,000.

This is a Division of application Ser. No. 08/080,785 filed on Jun. 24,1993, now U.S. Pat. No. 5,434,231, which is a Division of applicationSer. No. 07/949,156, filed on Sep. 23, 1992, now U.S. Pat. No.5,264,507.

The present invention relates to novel azo dye polymers containing ascharacteristic monomer units radicals of the formulae I, II, III and IV##STR2## where D is the radical of a diazo component derived from afive-membered aromatic heterocyclic amine having one to three heteroatoms selected from the group consisting of nitrogen, oxygen and sulfurin the heterocyclic ring and optionally fused to a benzene, thiophene,pyridine or pyrimidine ring,

R¹ and R² are each independently of the other hydrogen, C₁ -C₆ -alkyl orC₁ -C₆ -alkoxyoptionally substituted by phenyl or C₁ -C₄ -alkoxy, and R²may also be C₁ -C₄ -alkanoylamino,

R³ is hydrogen, C₁ -C₆ -alkyl, C₅ -C₇ -cycloalkyl or C₃ -C₄ -alkenyl,

R⁴ is hydrogen, deuterium, methyl, trideuterated methyl or chlorine,

R⁵ is hydrogen or deuterium,

Y¹ and Y² are each independently of the other C₂ -C₁₀ -alkyleneoptionally interrupted by 1 to 3 oxygen atoms in the ether function orimino or C₁ -C₄ -alkylimino groups,

W is oxygen, imino or C₁ -C₄ -alkylimino, and

X is hydroxyl, C₁ -C₆ -alkoxy, trideunerated methoxy, 2,3-epoxypropoxy,phenoxy, amino or C₁ -C₄ -mono- or -dialkylamino,

the proportion of monomer units of the formula I being from 1 to 100 mol%, the proportion of monomer units of the formula II being from 0 to 99mol %, the proportion of monomer units of the formula III being from 0to 99 mol % and the proportion of monomer units of the formula IV beingfrom 0 to 75 mol %, each percentage being based on the polymer, and theaverage molecular weight of the polymer being from 1,000 to 100,000, tothe use thereof in nonlinear optics and to the use of monomeric azo dyesfor preparing the novel polymers.

J. Polymer Sci., Part A, Polymer Chem. 28 (1990), 1-13, disclosespolymers with azo dye chromophores in the side chains. The azo dyesthere are members of the azobenzene series. However, it has been foundthat such polymers are still deficient when used in nonlinear opticalsystems.

It is an object of the present invention to provide novel polymers whichlikewise possess donor/acceptor-substituted azo dyes as chromophore inthe side chain and which shall be advantageous for use in nonlinearoptical systems.

We have found that this object is achieved by the azo dye polymersdefined at the beginning.

Suitable radicals D in the formula I are derived for example from aheterocyclic amine of the pyrrole, furan, thiophene, pyrazole,imidazole, oxazole, isoxazole, thiazole, isothiazole, triazole,oxadiazole, thiadiazole, benzofuran, benzothiophene, benzimidazole,benzoxazole, benzisothiazole, pyridothiophene, pyrimidothiophene,thienothiophene or thienothiazole series.

Of particular suitability are those radicals D derived from aheterocyclic amine of the pyrrole, thiophene, pyrazole, thiazole,isothiazole, triazole, thiadiazole, benzothiophene, benzothiazole,benzisothiazole, pyridothiophene, pyrimidothiophene, thienothiophene orthienothiazole series.

Of particular note are radicals D derived from aminoheterocycles of theformulae ##STR3## where L¹ is nitro, cyano, C₁ -C₆ -alkanoyl, benzoyl,C₁ -C₆ -alkylsulfonyl, substituted or unsubstituted phenylsulfonylsulfonyl or a radical of the formula --CH═T, where T is the radical ofan acidic CH compound,

L² is hydrogen, C₁ -C₆ -alkyl, halogen, hydroxyl, mercapto,unsubstituted or phenyl- or C₁ -C₄ -alkoxy-substituted C₁ -C₆ -alkoxy,substituted or unsubstituted phenoxy, unsubstituted orphenyl-substituted C₁ -C₆ -alkylthio, substituted or unsubstitutedphenylthio, C₁ -C₆ -alkylsulfonyl or substituted or unsubstitutedphenylsulfonyl,

L³ is cyano, C₁ -C₄ -alkoxycarbonyl or nitro,

L⁴ is hydrogen, C₁ -C₆ -alkyl or phenyl,

L⁵ is C₁ -C₆ -alkyl or phenyl,

L⁶ is cyano, C₁ -C₄ -alkoxycarbonyl, C₁ -C₆ -alkanoyl or halogen,

L⁷ is nitro, cyano, C₁ -C₆ -alkanoyl, benzoyl, C₁ -C₆ -alkylsulfonyl,substituted or unsubstituted phenylsulfonyl or a radical of the formula--CH═T, where T is as defined above,

L⁸ is hydrogen, C₁ -C₆ -alkyl, halogen, unsubstituted or phenyl- or C₁-C₄ -alkoxy-substituted C₁ -C₆ -alkoxy, unsubstituted orphenyl-substituted C₁ -C₆ -alkylthio, substituted or unsubstitutedphenylthio, C₁ -C₆ -alkylsulfonyl, substituted or unsubstitutedphenylsulfonyl or C₁ -C₄ -alkoxycarbonyl,

L⁹ is cyano, unsubstituted or phenyl-substituted C₁ -C₆ -alkyl,unsubstituted or phenyl-substituted C₁ -C₆ -alkylthio, substituted orunsubstituted phenyl, thienyl, C₁ -C₄ -alkylthienyl, pyridyl or C₁ -C₄-alkylpyridyl,

L¹⁰ is phenyl or pyridyl,

L¹¹ is trifluoromethyl, nitro, C₁ -C₆ -alkyl, phenyl, unsubstituted orphenyl-substituted C₁ -C₆ -alkylthio or C₁ -C₄ -dialkylamino,

L¹² is C₁ -C₆ -alkyl, phenyl, 2-cyanoethylthio or 2-(C₁ -C₄-alkoxycarbonyl)ethylthio,

L¹³ is hydrogen, nitro or halogen, and

L¹⁴ is hydrogen, cyano, nitro or halogen.

Any substituted phenyl appearing in the azo dye polymers according tothe invention may have as substituents for example C₁ -C₄ -alkyl, C₁ -C₄-alkoxy or halogen, in particular chlorine or bromine. These phenylrings will in general have from 1 to 3 substituents.

Any alkyl, alkylene or alkenyl groups appearing in the abovementionedformulae may be not only straight-chain but also branched.

R¹, R², R³, L², L⁴, L⁵, L⁸, L⁹, L¹¹ and L¹² are each for example methyl,ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl,neopentyl, tert-pentyl, hexyl or 2-methylpentyl.

R² may also be for example formylamino, acetylamino, propionylamino orbutynylamino.

L⁹ may also be for example benzyl or 1, or 2phenylethyl.

L², L⁸, L⁹ and L¹¹ may each also be for example methylthio, ethylthio,propylthio, isopropylthio, butylthio, isobutylthio, pentylthio,hexylthio, benzylthio or 1- or 2-phenylethylthio.

L² and L⁸ may each also be for example phenylthio, 2-methylphenylthio,2-methoxyphenylthio or 2-chlorophenylthio.

R¹, R², L² and L⁸ and also X may each also be for example methoxy,ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy,isopentyloxy, neopentyloxy, tert-pentyloxy, hexyloxy or2-methylpentyloxy.

L², L⁸, L¹³ and L¹⁴ and also L⁶ may each also be for example fluorine,chlorine or bromine.

L¹, L² and L⁸ and also L⁷ may each also be for example methylsulfonyl,ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl,isobutylsulfonyl, sec-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl,neopentylsulfonyl, hexylsulfonyl, phenylsulfonyl,2-methylphenylsulfonyl, 2-methoxyphenylsulfonyl or2-chlorophenylsulfonyl.

L⁶ and L⁸ and also L³ may each also be for example methoxycarbonyl,ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butyoxycarbonyl,isobutoxycarbonyl or sec-butoxycarbonyl.

R¹, R², L² and L⁸ may each also be for example 2-methoxyethoxy,2-ethoxyethoxy, 2- or 3-methoxypropoxy, 2- or 3-ethoxypropoxy, 2- or4-methoxybutoxy, 2- or 4-ethoxybutoxy, 5-methoxypentyloxy,5-ethoxypentyloxy, 6-methoxyhexyloxy, 6-ethoxyhexyloxy, benzyloxy or 1-or 2-phenylethoxy.

X may also be for example methylamino, ethylamino, propylamino,isopropylamino or butylamino.

L¹¹ and X may each also be for example dimethylamino, diethylamino,dipropylamino, diisopropylamino, dibutylamino or N-methyl-N-ethylamino.

L¹² may also be for example 2-methoxycarbonylethylthio or2-ethoxycarbonylethylthio.

R³ may also be for example cyclopentyl, cyclohexyl, cycloheptyl, allylor methallyl.

L⁹ may also be for example phenyl, 2-, 3- or 4-methylphenyl,2,4-dimethylphenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-methoxyphenyl,2- or 3-methylthienyl or 2-, 3- or 4-methylpyridyl.

Y¹ and Y² are each for example (CH₂)₂, (CH₂)₃, (CH₂)₄, (CH₂)₅, (CH₂)₆,(CH₂)₇, (CH₂)₈, (CH₂)₉, (CH₂)₁₀, CH(CH₃)--CH₂, CH(CH₃)--CH(CH₃), C₂ H₄--O--C₂ H₄, C₂ H₄ --NH--C₂ H₄ --N(CH₃)--C₂ H₄, C₂ H₄ O--C₂ H₄ --O--C₂H₄, C₂ H₄ --NH--C₂ H₄ --NH--C₂ H₄ --N(CH₃)--C₂ H₄ --N(CH₃)--C₂ H₄.

W is for example methylimino, ethylimino, propylimino, isopropylimino orbutylimino.

L¹, L⁶ and L⁷ may each also be for example formyl, acetyl, propionyl,butyryl, pentanoyl or hexanoyl.

When L¹ or L⁷ is the radical --CH═T wherein T is derived from an acidicCH compound H₂ T, include suitable acidic CH compounds H₂ T are forexample compounds of the formula ##STR4## where Z¹ is cyano, nitro, C₁-C₄ -alkanoyl, substituted or unsubstituted benzoyl, C₁ -C₄-alkylsulfonyl, substituted or unsubstituted phenylsulfonyl, carboxyl,C₁ -C₄ -alkoxycarbonyl, C₃ -C₄ -alkenyloxycarbonyl, phenoxycarbonyl,carbamoyl, mono- or di(C₁ -C₄ -alkyl)carbamoyl, substituted orunsubstituted phenylcarbamoyl, substituted or unsubstituted phenyl,2-benzothiazolyl, 2-benzimidazolyl, 5-phenyl-1,3,4-thiadiazol-2-yl or2-hydroxyquinoxalin-3-yl,

Z² is C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or C₃ -C₄ -alkenyloxy,

Z³ is C₁ -C₄ -alkoxycarbonyl, C₃ -C₄ -alkenyloxycarbonyl,phenylcarbamoyl or 2-benzimidazolyl,

Z⁴ is cyano, C₁ -C₄ -alkoxycarbonyl or C₃ -C₄ -alkenyloxycarbonyl,

Z⁵ is hydrogen or C₁ -C₆ -alkyl,

Z⁶ is hydrogen, C₁ -C₄ -alkyl or phenyl and

Z⁷ is C₁ -C₄ -alkyl.

Preference must be given here to the radical derived from compounds ofthe formula VIIa, VIIb or VIIc wherein Z¹ is cyano, C₁ -C₄ -alkanoyl, C₁-C₄ -alkoxycarbonyl or C₃ -C₄ -alkenyloxycarbonyl, Z² is C₁ -C₄ -alkyl,C₁ -C₄ -alkoxy or C₃ -C₄ -alkenyloxy, Z³ is C₁ -C₄ -alkoxycarbonyl or C₃-C₄ -alkenyloxycarbonyl, and Z⁴ is cyano.

Particular emphasis must be given here to the radical derived fromcompounds of the formula VIIa, VIIb or VIIc wherein Z¹ is cyano, C₁ -C₄-alkoxycarbonyl or C₃ -C₄ -alkenyloxycarbonyl, Z² is C₁ -C₄ -alkoxy orC₂ -C₄ -alkenyloxy, Z³ is C₁ -C₄ -alkoxycarbonyl or C₃ -C₄-alkenyloxycarbonyl, and Z⁴ is cyano.

Preference is given to azo dye polymers which as characteristic monomerunits contain radicals of the formula Ia ##STR5## where D, R¹, R², R³,R⁴, Y and W are each as defined above, and of the abovementioned formulaII.

Preference is further given to azo dye polymers where D in formula I isderived from an amine of the formula VIa, VIb, VIc, VId, VIe, VIf, VImor VIn.

Preference is further given to azo dye polymers in which the proportionof monomer units of the formula I is from 4 to 50, in particular from 8to 25, mol %, the proportion of monomer units of the formula II is from51 to 96, in particular from 75 to 92, mol %, the proportion of monomerunits of the formula III is from 0 to 30, in particular from 0 to 15,mol % and the proportion of monomer units of the formula IV is from 0 to50, in particular from 0 to 20 mol %, each percentage being based on thepolymer, and the average molecular weight of the polymer is from 1500 to50,000, in particular from 2000 to 25,000.

Of particular suitability are azo dye polymers in which in the formula I

R¹ is hydrogen or C₁ -C₄ -alkoxy,

R² is C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or acetylamino,

R³ is C₁ -C₄ -alkyl,

R⁴ is hydrogen or methyl, and

Y¹ is C₂ -C₈ -alkylene, and in the formula II

R⁴ is hydrogen or methyl, and

X is C₁ -C₄ -alkoxy.

Particular preference is given to azo dye polymers in which D is derivedfrom amines of the thiophene or thiazole series, in particular fromthose of the formula VIb or VId.

Of special interest are azo dye polymers in which D is derived from anamine of the formula VI b or VId where

L¹ is nitro, cyano, C₁ -C₄ -alkanoyl or a radical of the formula --CH═T,where T is as defined above,

L² is hydrogen, C₁ -C₄ -alkyl or halogen,

L³ is cyano, C₁ -C₄ -alkoxycarbonyl or nitro,

L⁷ is nitro, cyano, C₁ -C₄ -alkanoyl or a radical of the formula --CH═T,where T is as defined above, and

L⁸ is hydrogen, C₁ -C₄ -alkyl or halogen.

To prepare the polymers of the invention, it is advantageous to employazo dyes of the formula V ##STR6## where D, R¹, R², R³, R⁴, Y and W areeach as defined above.

The novel polymers can be prepared by methods known per se, for exampleas described in J. Polymer Sci. (loc. cit.).

Conveniently, an azo dye of the formula V is reacted with an acryloylcompound of the formula VIII ##STR7## where R⁴ and X are each as definedabove, styrene and a cinnamic ester of the formula IX ##STR8## where Y²and R⁴ are each as defined above, in the above-mentioned molar ratio inan inert solvent (for example toluene or xylene) in the presence of afree radical initiator (for example azobisisobutyronitrile).

The azo dyes of the formula V are known per se and described for examplein EP-A-201,896, DE-A-3,108,077, U.S. Pat. No. 4,843,153 orGB-A-1,546,803 or can be obtained by the methods mentioned therein.

The azo dye polymers of the invention are advantageously suitable foruse in nonlinear optical systems (see for example Chemistry andIndustry, 1 Oct. 1990, pages 600 to 608).

They are particularly suitable for use in communications technology,electrooptical modulators (for example Mach-Zehnder Interferometers),optical switches, frequency mixing or waveguides.

The layers which contain the polymers of the present invention areprepared in the conventional manner, for example by wet or spin coatingwith a 5-15% by weight solution of the polymer in a solvent (for exampletetrachloroethane, methylene chloride or tetrahydrofuran).

Given a suitable substitution pattern (for example an epoxy structure)the novel polymers can also be crosslinked photochemically, thermally orby the action of electron beams.

The novel polymers are notable for good processibility into thin films,high purity, a narrow molecular weight distribution, good orientation inan electric field, good long-term stability, high glass transitiontemperatures and a high electro-optical coefficient.

The Examples which follow will further illustrate the invention.

I. PREPARATION OF MONOMERIC AZO DYES Dye 1

a) Preparation of coupling component

421 g (3.05 mol) of potassium carbonate were suspended in 240 ml ofwater together with 40 g (0.12 mol) of potassium iodide. With continuousstirring 169 g (1.2 mol) of N-ethyl-m-toluidine in 240 ml of isobutanolwere added, followed by 260 g (1.8 mol) of 6-chlorohexanol. Then thereaction mixture was heated to the boil. After 12 hours under reflux,the reaction mixture was cooled down to room temperature, 400 ml ofwater were added, and the aqueous phase was separated off. The organicphase was washed three times with 400 ml of water each time and driedover sodium sulfate, and the solvent was removed under reduced pressure.The residual oil was subjected to fractional distillation (157°-158° C.at 1.0 mbar). Yield: 231 g (82%).

47 g (0.2 mol) of N-ethyl-N-(6-hydroxyhexyl)-m-toluidine were dissolvedin 600 ml of dichloromethane. 42 ml of triethylamine and 2.4 g ofhydroquinone were added. The reaction solution was cooled down to 0°-5°C., and 38 ml (0.4 mol) of methacryloyl chloride in 100 ml ofdichloromethane were gradually added dropwise. This was followed by 2hours' stirring at that temperature, warming to room temperature and afurther 50 hours' stirring. As workup, the organic phase was washed with300 ml of saturated sodium bicarbonate solution .and then twice with 300ml of sodium chloride solution each time. After drying over sodiumsulfate and concentrating of the solvent, the crude product was purifiedby column chromatography over silica gel using 94:5 v/v toluene/methanolas mobile phase. Yield: 44 g (71%) of the aniline of the formula##STR9## b) Preparation of azo dye

6.4 (0.035 mol) of 2-amino-4-chloro-3,5-dicyanothiophene were suspendedin 100 ml of 17:3 v/v glacial acetic acid/propionic acid. Then 14 ml of85% by weight sulfuric acid were added dropwise at room temperature and6 ml of nitrosylsulfuric acid dropwise at 0° to 5° C. After stirring atfrom 0° to 5° C. for 3 hours, the resulting diazonium salt solution wasadded dropwise to 10.9 g (0.036 mol) of the coupling component describedunder a) in 300 g of ice-water, 20 ml of concentrated hydrochloric acidand 1 g of amidosulfuric acid at <5° C. and at pH 1-1.5. The pH wasmaintained at 1-1.5 by the dropwise addition of 20% by weight sodiumhydroxide solution. After stirring overnight at room temperature theprecipitated dye was filtered off with suction, washed with water, driedand chromatographed twice over silica gel using 95:5 v/v hexane/acetoneas mobile phase.

Yield: 10 g (57%) of the dye of the formula ##STR10##

C₂₅ H₂₈ N₅ SO₂ Cl (498.0) calculated: C 60.29 H 5.67 N 14.06 S 6.43 O6.43 found: C 60.31 H 5.75 N 13.99 S 6.40 O 6.43

The same method gives the dyes of the formula ##STR11## listed below inTable 1.

                                      TABLE 1                                     __________________________________________________________________________    Dye                                                                           No.                                                                              D                     Q.sup.1                                                                          Q.sup.2                                                                           Q.sup.3                                                                          n                                          __________________________________________________________________________     2                                                                                ##STR12##            H  C.sub.2 H.sub.5                                                                   CH.sub.3                                                                         2                                           3                                                                                ##STR13##            CH.sub.3                                                                         C.sub.2 H.sub.5                                                                   CH.sub.3                                                                         6                                           4                                                                                ##STR14##            H  C.sub.2 H.sub.5                                                                   CH.sub.3                                                                         2                                           5                                                                                ##STR15##            H  C.sub.2 H.sub.5                                                                   CH.sub.3                                                                         2                                           6                                                                                ##STR16##            H  C.sub.2 H.sub.5                                                                   CH.sub.3                                                                         2                                           7                                                                                ##STR17##            H  C.sub.2 H.sub.5                                                                   CH.sub.3                                                                         2                                           8                                                                                ##STR18##            CH.sub.3                                                                         C.sub.2 H.sub.5                                                                   CH.sub.3                                                                         6                                           9                                                                                ##STR19##            H  C.sub.2 H.sub.5                                                                   CH.sub.3                                                                         2                                          10                                                                                ##STR20##            H  C.sub.2 H.sub.5                                                                   CH.sub.3                                                                         2                                          11                                                                                ##STR21##            H  C.sub.2 H.sub.5                                                                   CH.sub.3                                                                         2                                          12                                                                                ##STR22##            CH.sub.3                                                                         C.sub.2 H.sub.5                                                                   CH.sub.3                                                                         2                                          13                                                                                ##STR23##            CH.sub.3                                                                         C.sub.2 H.sub.5                                                                   CH.sub.3                                                                         6                                          14                                                                                ##STR24##            CH.sub.3                                                                         C.sub.2 H.sub.5                                                                   CH.sub.3                                                                         6                                          15                                                                                ##STR25##            H  C.sub.2 H.sub.5                                                                   CH.sub.3                                                                         2                                          16                                                                                ##STR26##            CH.sub.3                                                                         C.sub.2 H.sub.5                                                                   CH.sub.3                                                                         6                                          17                                                                                ##STR27##            CH.sub.3                                                                         C.sub.2 H.sub.5                                                                   CH.sub.3                                                                         6                                          18                                                                                ##STR28##            CH.sub.3                                                                         C.sub.2 H.sub.5                                                                   CH.sub.3                                                                         6                                          19                                                                                ##STR29##            CH.sub.3                                                                         C.sub.2 H.sub.5                                                                   CH.sub.3                                                                         6                                          __________________________________________________________________________

II. PREPARATION OF POLYMER

General polymerization method for preparing polyacrylates of thefollowing formula: ##STR30##

In a Schlenk vessel, a monomer solution comprising n mol % of dyemonomer and l+p+q mol % of comonomer in absolute toluene was admixedwith 2 mol % of azobisisobutyronitrile. After argon had been passedthrough the monomer mixture for 10 minutes, the monomer mixture wasthermostabilized at 50° C. The polymerization was complete after 100hours. The polymers were precipitated with methanol and reprecipitatedtwice from hexane/methanol. (If monomer is still present, it can beseparated off by column chromatography over silica gel, for exampleusing 9:1 v/v toluene/ethyl acetate as mobile phase.) After the solventhad been removed, the polymer was dried in a high vacuum. Thequantitative composition of the copolymers was determined by means of UVspectroscopy and elemental analysis. The molecular weights weredetermined by gel permeation chromatography. The glass transitiontemperature of the polymer was determined by differential scanningcalorimetry.

                                      TABLE 2                                     __________________________________________________________________________                                      Average                                     Example                       Dye molecular                                                                           T.sub.g                               No.  l m  p  q  Q.sup.4                                                                          Q.sup.5  Q.sup.6                                                                         No. weight                                                                              [°C.]                          __________________________________________________________________________     1   90                                                                              10 0  0  CH.sub.3                                                                         CH.sub.3 H 9   16807 125                                    2   90                                                                              10 0  0  CH.sub.3                                                                         CH.sub.3 H 3   22491 120                                    3   90                                                                              10 0  0  CH.sub.3                                                                         CH.sub.3 H 5   11594 151                                    4   90                                                                              10 0  0  CH.sub.3                                                                         CH.sub.3 H 10   3770 105                                    5   90                                                                              10 0  0  CH.sub.3                                                                         CH.sub.3 H 11   2661  95                                    6   80                                                                              20 0  0  CH.sub.3                                                                         CH.sub.3 H 2   13072 150                                    7   80                                                                              20 0  0  CH.sub.3                                                                         CH.sub.3 H 3   11062 155                                    8   88                                                                              12 0  0  CH.sub.3                                                                         CH.sub.3 H 3   11489 145                                    9   90                                                                              10 0  0  CH.sub.3                                                                         CH.sub.3 H 6                                               10   90                                                                              10 0  0  CH.sub.3                                                                         CH.sub.3 H 13  14685  86                                   11   90                                                                              10 0  0  CH.sub.3                                                                          ##STR31##                                                                             H 2   13434 125                                   12   90                                                                              10 0  0  CO.sub.3                                                                         CO.sub.3 O 3   18384 130                                   13   80                                                                              10 0  10 CH.sub.3                                                                         CH.sub.3 H 3                                               14   80                                                                              10 10 0  CH.sub.3                                                                         CH.sub.3 H 3    2877                                       15   50                                                                              50 0  0  CH.sub.3                                                                         CH.sub.3 H 3                                               16    0                                                                              100                                                                              0  0  CH.sub.3                                                                         CH.sub.3 H 3                                               17   90                                                                              10 0  0  CH.sub.3                                                                         CH.sub.3 H 17         90                                   18   90                                                                              10 0  0  CH.sub.3                                                                         CH.sub.3 H 18        100                                   __________________________________________________________________________

We claim:
 1. A method for the preparation of an azo dye polymercontaining as characteristic monomer units radicals of the formulae I,II, III and IV ##STR32## where D is the radical of the diazo componentderived from a pyrrole, furan, thiophene, pyrazole, imidazole, oxazole,isoxazole, thiazole, isothiazole, triazole, oxadiazole, thiadiazole,benzofuran, benzothiophene, benzimidazole, benzoxazole, benzisothiazole,pyridothiophene, pyrimidothiophene or thienothiophene,R¹ and R² are eachindependently of the other hydrogen, C₁ -C₆ -alkyl or C₁ -C₆ -alkoxyoptionally substituted by phenyl or C₁ -C₄ -alkoxy, and R² may also beC₁ -C₄ -alkanoylamino, R³ is hydrogen, C₁ -C₆ -alkyl, C₅ -C₇ -cycloalkylor C₃ -C₄ -alkenyl, R⁴ is hydrogen, deuterium, methyl, trideuteratedmethyl or chlorine, R⁵ is hydrogen or deuterium, Y¹ and Y² are eachindependently of the other C₂ -C₁₀ -alkylene optionally interrupted by 1to 3 oxygen atoms in the ether function or imino or C₁ -C₄ -alkyliminogroups, W is oxygen, imino or C₁ -C₆ -alkylimino, and X is hydroxyl, C₁-C₆ -alkoxy, trideuterated methoxy, 2,3-epoxypropoxy, phenoxy, amino orC₁ -C₄ -mono- or -dialkylamino, the proportion of monomer units of theformula I being from 1 to 100 mol %, the proportion of monomer units ofthe formula II being from 0 to 99 mol %, the proportion of monomer unitsof the formula III being from 0 to 99 mol % and the proportion ofmonomer units of the formula IV being from 0 to 75 mol %, eachpercentage being based on the polymer, and the average molecular weightof the polymer being from 1,000 to 100,000, comprising polymerizing acompound of the formula (V) ##STR33## optionally with at least onecompound of the formula (VIII), (IX) or styrene ##STR34## in thepresence of a free radical initiator, wherein D, R¹, R², R³, R⁴, R⁵, Y¹,Y², W and X are as above defined.